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ISSN: 2056-9890

3-(1H-Tetra­zol-5-yl)benzoic acid

aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, People's Republic of China, and bDepartment of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 211189, People's Republic of China
*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 8 December 2008; accepted 8 December 2008; online 10 December 2008)

The title compound, C8H6N4O2, is a difunctional compound with a carboxyl­ate and a tetra­zole residue. In the crystal structure, mol­ecules are linked into two-dimensional sheets by inter­molecular N—H⋯O and O—H⋯N hydrogen bonds.

Related literature

For the applications of tetra­zoles, see: Chen & Tong (2007[Chen, X.-M. & Tong, M.-L. (2007). Acc. Chem. Res. 40, 162-170.]); Demko & Sharpless (2001[Demko, Z. P. & Sharpless, K. B. (2001). J. Org. Chem. 66, 7945-7950.]). For related structures, see: Rizk et al. (2005[Rizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359-362.]).

[Scheme 1]

Experimental

Crystal data
  • C8H6N4O2

  • Mr = 190.17

  • Monoclinic, P 21 /c

  • a = 5.2501 (10) Å

  • b = 16.805 (3) Å

  • c = 9.3290 (18) Å

  • β = 99.188 (3)°

  • V = 812.5 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.12 mm−1

  • T = 293 (2) K

  • 0.45 × 0.14 × 0.13 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan SADABS (Sheldrick, 2000[Sheldrick, G. M. (2000). SADABS, University of Göttingen.]) Tmin = 0.949, Tmax = 0.985

  • 5991 measured reflections

  • 1583 independent reflections

  • 1425 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.106

  • S = 1.07

  • 1583 reflections

  • 136 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.24 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2B⋯N4i 0.93 (2) 1.76 (2) 2.6664 (15) 164 (2)
N1—H1A⋯O1ii 0.94 (2) 1.77 (2) 2.7118 (16) 179.1 (19)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Tetrazoles have been extensively investigated in organic synthetic chemistry for several decades due to the fact that they have wide ranging applications in pharmaceuticals, especially explosives, photography, information recording systems, agriculture, and as precursors to a variety of heterocycles (Chen et al. 2007; Demko et al. 2001). They have also been used as a type of important multidentate ligands in coordination chemistry. Here, we report the crystal structure of a new tetrazole, 3-(1H-tetrazol-5-yl)benzoic acid.

The title compound, C8H6N4O2, is a difunctional compound with carboxylate and tetrazole groups. The C=O distance of the carboxylate is 1.216 (2) Å, which is much shorter than the C—O distance of 1.311 (2) Å. In the tetrazole group, the N=N distance is 1.288 (2) Å, and the N—N distances are 1.343 (2) and 1.358 (2) Å, respectively. The C—N distance is 1.333 (2) Å, being close to the C=N distance of 1.325 (2) Å, which is considered to have part double-bond character. In the crystalline state, the molecules are linked to two-dimensional hydrogen-bonding networks by intermolecular N—H···O and O—H···N hydrogen bonds. The N···O distance is 2.712 (2) Å, and the O···N distance is 2.666 (2) Å.

Related literature top

For the applications of tetrazoles, see: Chen & Tong (2007); Demko & Sharpless (2001). For related structures, see: Rizk et al. (2005).

Experimental top

A mixture of 3-cyanobenzoic acid (0.147 g, 1.0 mmol), Cd(NO3)2.6H2O (0.345 g, 1 mmol) and water (8 ml) was was heated in a 15-ml Teflon-lined autoclave at 160 ° for 3 days, followed by slow cooling (5 ° h-1) to room temperature. The resulting mixture was washed with water and collected. Then, the obtained solids were put into 20 ml water, and 10% Na2S aqueous solution was droped to the suspension liquid until that no precipitation appeared. The solution was filtered and the filtrate was acidified with 50% HCl solution until the pH value was 1.0. White products were filtered, washed with water, then dried and collected in 76.2% yield (0.145 g) based on 3-cyanobenzoic acid. Colorless block shaped crystals were collected from the filtrate after the second filtration.

Refinement top

H atoms bonded to N and O atoms were located in a difference map and were freely refined. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and with Uiso(H) = 1.2.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: SHELXTL Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Structure of the title compound with 30% displacement ellipsoids.
[Figure 2] Fig. 2. The two-dimensional hydrogen bonding network of the title compound.
[Figure 3] Fig. 3. Packing of the title compound with view onto the ac plane.
(I) top
Crystal data top
C8H6N4O2F(000) = 392
Mr = 190.17Dx = 1.555 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 785 reflections
a = 5.2501 (10) Åθ = 2.4–28.0°
b = 16.805 (3) ŵ = 0.12 mm1
c = 9.3290 (18) ÅT = 293 K
β = 99.188 (3)°Block, colorless
V = 812.5 (3) Å30.45 × 0.14 × 0.13 mm
Z = 4
Data collection top
Bruker APX CCD
diffractometer
1583 independent reflections
Radiation source: fine-focus sealed tube1425 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
phi and ω scanθmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan
SADABS (Sheldrick, 2000)
h = 66
Tmin = 0.949, Tmax = 0.985k = 2020
5991 measured reflectionsl = 1111
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.0592P)2 + 0.1634P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1583 reflectionsΔρmax = 0.19 e Å3
136 parametersΔρmin = 0.24 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.018 (3)
Crystal data top
C8H6N4O2V = 812.5 (3) Å3
Mr = 190.17Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.2501 (10) ŵ = 0.12 mm1
b = 16.805 (3) ÅT = 293 K
c = 9.3290 (18) Å0.45 × 0.14 × 0.13 mm
β = 99.188 (3)°
Data collection top
Bruker APX CCD
diffractometer
1583 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 2000)
1425 reflections with I > 2σ(I)
Tmin = 0.949, Tmax = 0.985Rint = 0.018
5991 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.19 e Å3
1583 reflectionsΔρmin = 0.24 e Å3
136 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.0644 (2)0.36005 (6)0.68049 (12)0.0471 (3)
O20.3759 (2)0.42002 (6)0.58687 (13)0.0496 (3)
H2B0.410 (4)0.3707 (14)0.550 (2)0.082 (7)*
C10.1794 (3)0.42040 (8)0.65768 (15)0.0358 (3)
C20.1127 (3)0.50146 (7)0.70380 (15)0.0349 (3)
C30.0705 (3)0.51184 (8)0.79498 (16)0.0403 (4)
H3A0.14990.46800.82960.048*
C40.1332 (3)0.58797 (9)0.83368 (16)0.0439 (4)
H4A0.25390.59500.89550.053*
C50.0189 (3)0.65372 (8)0.78180 (16)0.0392 (3)
H5A0.06400.70460.80810.047*
C60.1642 (3)0.64386 (7)0.68994 (14)0.0338 (3)
C70.2301 (2)0.56732 (8)0.65297 (14)0.0356 (3)
H7A0.35440.56020.59340.043*
C80.2910 (3)0.71171 (7)0.63149 (14)0.0338 (3)
N10.2597 (2)0.78846 (7)0.66034 (13)0.0402 (3)
N20.4101 (3)0.83282 (7)0.58804 (14)0.0453 (3)
N30.5310 (3)0.78398 (7)0.51637 (14)0.0445 (3)
N40.4608 (2)0.70804 (7)0.54077 (13)0.0394 (3)
H1A0.147 (4)0.8129 (12)0.716 (2)0.067 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0573 (7)0.0296 (5)0.0618 (7)0.0056 (4)0.0317 (5)0.0017 (4)
O20.0616 (7)0.0266 (5)0.0718 (7)0.0021 (4)0.0446 (6)0.0037 (5)
C10.0416 (7)0.0290 (7)0.0408 (7)0.0007 (5)0.0188 (6)0.0037 (5)
C20.0379 (7)0.0299 (7)0.0400 (7)0.0007 (5)0.0158 (6)0.0010 (5)
C30.0448 (8)0.0328 (7)0.0485 (8)0.0023 (6)0.0231 (6)0.0013 (6)
C40.0468 (8)0.0408 (8)0.0510 (8)0.0015 (6)0.0285 (7)0.0021 (6)
C50.0434 (8)0.0305 (7)0.0474 (8)0.0036 (5)0.0188 (6)0.0048 (6)
C60.0374 (7)0.0285 (7)0.0380 (7)0.0004 (5)0.0133 (5)0.0002 (5)
C70.0394 (7)0.0311 (7)0.0406 (7)0.0002 (5)0.0195 (6)0.0003 (5)
C80.0383 (7)0.0266 (6)0.0388 (7)0.0026 (5)0.0131 (5)0.0021 (5)
N10.0498 (7)0.0263 (6)0.0496 (7)0.0012 (5)0.0238 (6)0.0017 (5)
N20.0564 (8)0.0290 (6)0.0559 (8)0.0022 (5)0.0257 (6)0.0001 (5)
N30.0537 (7)0.0293 (6)0.0562 (8)0.0026 (5)0.0260 (6)0.0005 (5)
N40.0470 (7)0.0263 (6)0.0504 (7)0.0010 (5)0.0247 (5)0.0010 (5)
Geometric parameters (Å, º) top
O1—C11.2163 (16)C5—H5A0.9300
O2—C11.3112 (16)C6—C71.3898 (18)
O2—H2B0.93 (2)C6—C81.4684 (18)
C1—C21.4871 (18)C7—H7A0.9300
C2—C71.3868 (18)C8—N41.3254 (17)
C2—C31.3927 (19)C8—N11.3331 (17)
C3—C41.3833 (19)N1—N21.3430 (16)
C3—H3A0.9300N1—H1A0.94 (2)
C4—C51.381 (2)N2—N31.2882 (17)
C4—H4A0.9300N3—N41.3576 (16)
C5—C61.3961 (18)
C1—O2—H2B114.1 (14)C7—C6—C5119.03 (12)
O1—C1—O2122.47 (12)C7—C6—C8118.74 (11)
O1—C1—C2124.52 (12)C5—C6—C8122.22 (12)
O2—C1—C2113.01 (11)C2—C7—C6120.79 (12)
C7—C2—C3119.79 (12)C2—C7—H7A119.6
C7—C2—C1119.61 (11)C6—C7—H7A119.6
C3—C2—C1120.59 (11)N4—C8—N1106.91 (11)
C4—C3—C2119.44 (12)N4—C8—C6126.31 (11)
C4—C3—H3A120.3N1—C8—C6126.77 (12)
C2—C3—H3A120.3C8—N1—N2109.54 (11)
C5—C4—C3120.91 (12)C8—N1—H1A129.9 (12)
C5—C4—H4A119.5N2—N1—H1A120.5 (12)
C3—C4—H4A119.5N3—N2—N1106.56 (11)
C4—C5—C6120.02 (12)N2—N3—N4110.02 (11)
C4—C5—H5A120.0C8—N4—N3106.96 (10)
C6—C5—H5A120.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2B···N4i0.93 (2)1.76 (2)2.6664 (15)164 (2)
N1—H1A···O1ii0.94 (2)1.77 (2)2.7118 (16)179.1 (19)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC8H6N4O2
Mr190.17
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)5.2501 (10), 16.805 (3), 9.3290 (18)
β (°) 99.188 (3)
V3)812.5 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.45 × 0.14 × 0.13
Data collection
DiffractometerBruker APX CCD
diffractometer
Absorption correctionMulti-scan
SADABS (Sheldrick, 2000)
Tmin, Tmax0.949, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
5991, 1583, 1425
Rint0.018
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.106, 1.07
No. of reflections1583
No. of parameters136
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.24

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS (Sheldrick, 2008), SHELXL (Sheldrick, 2008), SHELXTL Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2B···N4i0.93 (2)1.76 (2)2.6664 (15)164 (2)
N1—H1A···O1ii0.94 (2)1.77 (2)2.7118 (16)179.1 (19)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1/2, z+3/2.
 

Acknowledgements

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

References

First citationBruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChen, X.-M. & Tong, M.-L. (2007). Acc. Chem. Res. 40, 162–170.  Web of Science CrossRef PubMed CAS Google Scholar
First citationDemko, Z. P. & Sharpless, K. B. (2001). J. Org. Chem. 66, 7945–7950.  Web of Science CrossRef PubMed CAS Google Scholar
First citationRizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359–362.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2000). SADABS, University of Göttingen.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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